Photographic products



E. H. LAND PHOTOGRAPHIC PRODUCTS Original Filed March 21. 1957 Feb. 11, 1964 United States Patent It) Claims. (Cl. 95-90) The present invention relates to photographic products and, more particularly, to products for treating an exposed silver halide emulsion in a novel manner.

This application is a division of copending application, Serial No. 647,675, filed March 21, 1957, now abandoned in favor of application Serial No. 212,072, filed July 24, 1962.

The primary objects of the present invention are: to provide, as a novel product, a container having two openings defined by two pairs of Squeegees through which an elongated strip of material may be advanced into and out of the container without escape of the fluid carried thereby; and to use a container of the foregoing type in photographic processes.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the product possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.

For a fuller understanding of the nature and objects of the invention, reference should be had to the following detailed description taken in connection with the accompanying drawing wherein:

FIGURE 1 is a perspective view, partly broken away, of the container of a product incorporating the present invention; and

FIG. 2 is a perspective View of the container of FIG. 1 in operation.

One preferred form of the container of the present invention is shown in FIGS. 1 and 2 and comprises an elongated open-topped housing it). Housing in comprises rectangular side walls 12, 12 slightly greater in height than a strip 14 (PEG. 2), such as of latent images to be treated, is in width. Side walls l2, 12 are joined by a bottom wall 16 and end walls 1-8 and Ztl providing openings 22 and 24 that communicate with the housings open top. Housing Iltl preferably is formed of a rigid material such as a stainless metal or an alkali-resistant plastic. At the top of the housing is a closure 26 hinged at 28 and 3%. Closure 26 is adapted to be locked in registration with the upper edges of side walls 12, 12 and end Walls 1'8, 2% by means of a toggle clamp 32, 34.

Two pairs of squeegees 36, 38 and 4% 42 define fluidtight slits 46, 48 through which a strip material such as a film may be introduced to and removed from housing 10. These Squeegees, which in conventional fashion are composed of a rubber or rubberlike material, are held in position between retainers 50, and 52, 52 and between retainers 54, 54 and end wall 20. These pairs of squeegees resiliently press against a leader 56 and each other to provide a barrier which substantially prevents escape of the fluid from within the container. A pair of moistureabsorbent lips 5%, so are held in position between retainers 50, 50 and end wall =18. These lips, which are charged with water or some other suitable liquid, are provided for the purpose of wetting the opposed surfaces of strip 14 before advancing between elements 36 and 38 in order to prevent their being scratched. When a silver halide stratum is tobe introduced between Squeegees 36 and 3?, the liquid preferably incorporates a hardening 3,l2h,795 Patented Feio. ll, 1%64 ice agent, such as sodium sulfate, chrome alum, acrolein, aldehydes such as formaldehyde, and diketones such as ethyl methyl ketone, for the purpose of obviating any possibility of harming the silver halide stratum as it advances. As shown in FIG. 1, initially a leader 56 composed, for example, of a waterproof paper or plastic extends through housing ltl. As shown in full lines, the rearward end 62 of leader 56 is curled upon itself for convenient storage in the slot between the spaced portions of wall 18. As shown in dotted lines, the rearward end of leader 56 is provided with flaps 64 and 66 the inner surfaces of which are provided with a pressure-sensitive adhesive. In practice, the leading end of strip 14 is secured by manual pressure between the elements of this bifurcated flap so that strip 14 may be advanced through compartment ltl thereafter. Similarly, the forward end 68 of leader 56 is initially curled upon itself in the slot between the spaced portions of wall 20. In storage, slots 22 and 2-4 are covered by strips 7% and 72 of pressure-sensitive adhesive initially adhering to portions of walls 18 and 2t) surrounding the slots for the purpose of hermetically sealing the interior of compartment it) and retaining the liquid within lips 58 and 60.

Bottom wall 16 is provided with an opening 74 in which is secured a relatively flexible membrane 76 capable of transmitting energy from a vibrator 78. Vibrator 78 is removably afiixed to the underfa'ce of lower wall 16 by guides so.

A pair of sprockets 82 and 84 are provided to advance strip 14 at a predetermined speed through container ltl, by virtue of which successive sections of the strip remain within the chamber for a requisite predetermined processing or treating period.

The use of the above-described container will be further illustrated by the following nonlimiting example.

Example 1 A strip of 35 mm. motion picture film, that had been exposed in conventional fashion, is continuously advanced, as shown in FIG. 2, through container 10 which carries a processing composition, to yield a succession of clear motion picture frames. The processing composition is prepared from a Solution A which incorporates the following ingredients:

Water cc 1860 Sodium carboxymethyl cellulose (Hercules 1362 medium viscosity type) grarns 20 Sodium sulfite do 78 Sodium hydroxide do 74.6 Sodium thiosulfate do 50 Citric acid do 38.5 Hydroquinone ..do 52 Ohlorobenzotriazole do. 1.5

This Solution A is prepared under a nitrogen atmosphere as follows: The sodium carboxymethyl cellulose is dis solved in the water in a mixer at room temperature. Thereafter, the sodium sulfite, sodium hydroxide, sodium thiosulfate and citric acid are added to the solution. The hydroqninone then is added and the composition mixed for an hour at approximately room temperature in a nitnogen atmosphere.

To 60 grams of Solution A there is then added 2 cc. of a fresh 1% aqueous sodium sulfide solution.

After a thorough mixing, there is added slowly, drop by drop, a Solution B which comprises Water cc 2 Lead acetate "gram" 0.016 Cadmium acetate do 0.011

As exemplified above, the container of the present invention is particularly useful for the processing of successive silver halide latent images produced, for example, by photoexposure through a lens in any suitable way. Such an image is formed in a silver halide stratum that is laminated to a support. The successive areas or sections of this stratum are immersed successively in a fluid suspensoin having an external or continuous phase containing an aqueous alkaline solution of a silver halide developer and a silver halide solvent, and an internal or discontinuous phase containing suspended solid particles. The developer and the solvent act throughout the silver halide stratum to reduce exposed silver halide to silver and to react with unreduced silver halide to form a soluble complex silver salt. The solid particles serve as precipitation nuclei, at which development of the complex salt to silver occurs at a rate that substantially precludes its return to the negative. The solid particles are maintained in suspension by any suitable dissolved natural, synthetic or other dispersing agent. The quantity of fluid is great enough to be substantially maintained at a predetermined magnitude, notwithstanding the absorption of relatively minute proportions of its external phase by the latent images processed thereby. Preferably the fluid suspension is agitated while the silver halide stratum is immersed therein in order to ensure free circulation of the developer and the solvent between the latent image and the dispersed solid particles. During the processing period the antihalation layer, with which the supported silver halide emulsion usually is provided, either bleaches or dissolves.

In one form, the external or continuous phase of the fluid is an aqueous alkaline solution of a silver halide developer and a silver halide solvent. Suitable developers are: benzene derivatives having at least two hydroxyl and/or amino groups substituted in ortho or para position on the benzene nucleus, such as hydroquinone, amidol, metol, glycin, para-aminophenol and pyrogallol; and hydroxylamines, in particular, primary and secondary aliphatic and aromatic N-substituted or fl-hydroxylamines which are soluble in aqueous alkali, including hydroxylamine, N-methyl hydroxyla mine, N-ethyl hydroxylamine, and others described in Patent No. 2,857,276, issued to Edwin H. Land et al. on October 21, 1958. Suitable silver halide solvents are: conventional fixing agents such as sodium thiosulfate, sodium thiocyanate, ammonium thiosulfate, and others described in Patent No. 2,543,181, issued to Edwin H. Land on February 27, 1951; and associations of cyclic imides and nitrogenous bases such as associations of barbiturates or uracils, and ammonia or amines, and other associations described in Patent No. 2,857,274, issued to Edwin H. Land et al. on October 21, 1958.

In general, the internal or discontinuous phase comprises solid minute particles of a substance which is insoluble in the external phase and which accelerates the r dl si b the d lo e o su h silver-bearing ions as are dissolved in the external phase. Substances most suitable for this purpose are insoluble inorganic particles, particularly metallic sulfides and selenides, e.g., lead sulfide, nickel sulfide, cobaltous sulfide, cupric sulfide, lead selenide and zinc selenide. Colloidal dispersions of metals such as silver and gold also are suitable for this purpose.

A wide range of polymeric materials may be dissolved in the fluid to maintain the internal phase and the external phase distinct. Examples of these polymeric materials are: vinyls such as polyvinyl alcohol; cellulosics such as methyl cellulose, ethyl cellulose, sodium carboxymethyl cellulose and cellulose acetate hydrogen phthalate; gums such as gum arabic; and proteins such as sodium alginate.

One form of silver halide stratum incorporates one or more of the silver halides, of which silver chloride, sliver bromide and silver iodide are examples, dispersed in a suitable protective colloid, for example gelatine, agar, albumen, casein, collodion, a cellulosic such as carboxymethyl cellulose, a vinyl polymer such as polyvinyl alcohol or a linear polyamide such as polyhexamethylene adipamide. Examples of specific formulations of con- .ventional emulsions suitable for such use are described in T. T. Baker, Photographic Emulsion Technique, American Photographic Publishing Company, Boston, 1948, chapter 4. This stratum is laminated to a support that may be composed of a suitable paper such as baryta paper, or a synthetic polymer such as nitrocellulose. When the support is composed of a polymer of the foregoing type, it is backed by an antihalation layer, which, for example, contains a dye that absorbs light actinic to the silver halide emulsion but which is decolorized or absorbed by the processing solution. Alternatively, the antihalation material capable of being bleached is incorporated in the support or between the support and the silver halide stratum. Conventional dyes for these pur poses include triphenyl methane dyes such as acid fuchsin and malachite green, colloidal inorganic compounds such as colloid manganese dioxide, and bleachable dyes such as indophenols and styryls.

The proportions of the ingredients of the processing fluid may be varied within wide limits. However, where the processing period is within the range of from 2 to 50 seconds, practical results are achieved where, by total Weight of the fluid, the developer ranges from 1 to 8%, the solvent from .3 to 10% and the precipitation nuclei from .5 to 3%. For most rapid results, the molar concentration of the solvent should be from two to five times the molar concentration of the developer.

Although the container of the present invention is particularly useful for the continuous development and fixation of exposed silver halide emulsions, it is obvious that a it is applicable for use in other photographic processes.

Since certain changes may be made in the above product without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description or shown in the accompanying drawing shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

1. A photographic product comprising a container having a pair of opposed openings therein, a silver halide developing fluid carried by said container, said fluid extended to and being confined between said pair of openings, one of said openings being defined by an outer pair of fluid absorbent lips and an inner pair of squeegees between which a gelatino silver halide emulsion may be inserted into said container without the escape of fluid therefrom, said lips being charged with a liquid adapted to Wet the opposing surfaces of said gelatino silver halide emulsion before said emulsion is inserted between said pair of equeegees, thereby preventing scratching of said emulsion, the other of said openings being defined by a pair of equeegees between which said gelatino silver halide emulsion may be withdrawn from said container Without the escape of fluid therefrom, said fluid containing an external phase including a silver halide developer and a silver halide solvent and an internal phase including solid particles.

'2. A photographic product comprising a container for holding a photographic fluid and having a pair of openin'gs therein, one of said openings being defined by an outer pair of fluid adsorbent lips and an inner pair of Squeegees, said lips and said Squeegees serving to receive a photographic strip advancing into said container while preventing the escape of photographic fluid therefrom, said lips being charged with a liquid adapted to wet the opposing surfaces of said photographic strip before said strip is received by said pair of Squee ees, thereby preventing scratching of said strip, the'other of said openings being defined by a pair of Squeegees between which said photographic strip may be withdrawn from said container while preventing the escape of photographic fluid therefrom.

3. A photographic product comprising a container having a pair of openings therein, a photographic fluid carried by said container, one of said openings being defined by an outer pair of fluid absorbent lips and an inner pair of Squeegees, said lips and said Squeegees serving to receive a photographic strip advancing into said container while preventing the escape of photographic fluid therefrom, said lips being charged with a liquid adapted to wet the opposing surfaces of said photographic strip before said strip is received by said pair of Squeegees, thereby preventing scratching of said strip, the other of said openings being defined by a pair of Squeegees between which said photographic strip may be withdrawn from said container While preventing the escape of photographic fluid therefrom, and a strip of moisture-impermeable tape covering said first opening externally thereof.

4. The photographic product of claim 3 wherein the inner surface of said strip is coated with a pressuresensitive adhesive.

5. A photographic product comprising a container having a pair of opposed openings therein, a silver halide developing fluid carried by said container, one of said openings being defined by an outer pair of fluid absorbent lips and an inner pair of Squeegees between which a gelatino silver halide emulsion may be inserted into said container without the escape of fluid therefrom, said lips being charged with a fluid containing a hardener for said gelatino silver halide emulsion advancing between said lips, the other of said openings being defined by a pair of Squeegees between which said gelatino silver halide emulsion may be withdrawn from said container without the escape of fluid therefrom, said fluid containing an external phase including a silver halide developer and a silver halide solvent and an internal phase including solid particles.

6. A photographic product comprising a container for t5 graphic strip advancing into said container while preventing the escape of photographic fluid therefrom, the other of said openings being defined by a pair of Squeegees between which said photographic strip may be withdrawn from said container while preventing the escape of photographic fluid therefrom, said lips being charged with a pretreating fluid for application to said photographic strip.

7. The photographic product of claim 6 wherein a strip of moisture-impermeable tape initially covers and seals said one of said openings.

8. A photographic product comprising a container for holding a photographic fluid and having a pair of openings therein, each of said openings being defined by a pair of Squeegees, a leader extending through each of said openings and through said container, one end of said leader having a bifurcated portion providing a pair of flaps the adjacent surfaces of which are coated with pressure-sensitive adhesive.

9. The photographic product of claim 8 wherein the ends of said leader outside of said container are folded upon themselves in order to occupy minimum space.

10. A photographic product comprising a container for holding a photographic fluid and having a pair of openings therein, one of said openings being defined by a first pair of Squeegees, the other of said openings being defined by an outer pair of fluid absorbent lips and an inner second pair of Squeegees, a leader extending through each of said openings and through said container, one end of said leader having a bifurcated portion providing a pair of flaps the adjacent surfaces of which are coated with pressure-sensitive adhesive.

References Cited in the file of this patent UNITED STATES PATENTS 2,382,868 Fink Apr. 14, 1945 2,522,071 Tait Sept. 12, 1950 2,894,440 Boger July 14, 195. 

6. A PHOTOGRAPHIC PRODUCT COMPRISING A CONTAINER FOR HOLDING A PHOTOGRAPHIC FLUID AND HAVING A PAIR OF OPENINGS THEREIN, ONE OF SAID OPENINGS BEING DEFINED BY AN OUTER PAIR OF FLUID ABSORBENT LIPS AND AN INNER PAIR OF SQUEEGEES, SAID LIPS AND SAID SQUEEGEES SERVING TO RECEIVE A PHOTOGRAPHIC STRIP ADVANCING INTO SAID CONTAINER WHILE PREVENTING THE ESCAPE OF PHOTOGRAPHIC FLUID THEREFROM, THE OTHER OF SAID OPENINGS BEING DEFINED BY A PAIR OF SQUEEGEES BETWEEN WHICH SAID PHOTOGRAPHIC STRIP MAY BE WITHDRAWN FROM SAID CONTAINER WHILE PREVENTING THE ESCAPE OF PHOTOGRAPHIC FLUID THEREFROM, SAID LIPS BEING CHARGED WITH A PRETREATING FLUID FOR APPLICATION TO SAID PHOTOGRAPHIC STRIP. 